Certain oxyalkylation products derived in turn from reactive nitrogen-containing compounds and polyepoxides, and process for making same



5,578,271 CERTAIN @XYALKYLATHQN PRGDUT DE- "1% i) [N TURN FROM REACTEVENITRO- GEN=CONTA1NHNG t3 6 M P 0 U N D S AND PGLYEPOXEDES, AND PRQCESSEUR MAKENG SAME Meivin De Groote, St. Louis, and Kevan-Ting Siren,Brentwood, Mo, assignors to hetrolite Corporation, Wiimington, Deh, acorporation of Delaware No Drawing. {)riginai application Aug. 26, 1953,Ser. No. 376,763, new Patent No. 2,81%,222, dated Ian. 7, 1958. Dividedand this application Dec. 6, 1956, Ser. No. 626,611

1 Claim. (61. 260-2475) The present invention is a continuation of ourcopending applications, Serial Nos. 305,079, now abandoned and 305,080,now Patent No. 2,723,241, both filed August 18, 1952 and a division ofour copending application Serial No. 376,763, filed August 26, 1953 andnow Patent No. 2,819,222.

Our invention is concerned with new chemical products H: H H:

or compounds useful as demulsifying agents in processes or proceduresparticularly adapted for preventing, breaking or resolving emulsions ofthe water-in-oil type and particularly petroleum emulsions. Ourinvention is also concerned with the application of such chemicalproducts or compounds in various other arts and industries as well aswith methods of manufacturing the new chemical products or compoundswhich are of outstanding value in demulsification.

The present invention may be characterized in one aspect in that it isconcerened with a process of oxyalkylating by means of monoepoxides, thereaction product obtained in turn by reacting certain monomericnon-resinous nitrogen-containing compounds, hereinafter described indetail, with certain phenolic polyepoxides, particularly diepoxides,also hereinafter described in detail, and cogenerically associatedcompounds formed in their preparation.

In preparing diepoxides or the low molal polymers one does usuallyobtain cogeneric materials which may include monoepoxides. However, thecogeneric mixture is invariably characterized by the fact that there ison the average, based on the molecular weight, of course, more than oneepoxide group per molecule.

A more limited aspect of the present invention is represented by theoxyalkylation products wherein the polyepoxide is represented by (1)Compounds of the following formula:

[mo-orr-om-o-Oi'o (CH3):

(2) Cogenerically associated compounds formed in the preparation of (1)preceding,

with the proviso that it consists principally of the monomer asdistinguished from other cogeners.

Not withstanding the fact that subsequent data will be presented inconsiderable detail, yet the description becomes somewhat involved andcertain facts should be kept in mind. The epoxides, and particularly thediepoxides, may have no connecting bridge between the phenolic nuclei asin the case of a diphenyl derivative or may have a variety of connectingbridges, i.e., divalent linking radicals. Our preference is that eitherdiphenyl compounds be employed or else compounds where the divalent linkis obtained by the removal of a carbonyl oxygen atom as derived from aketone or aldehyde.

33%?8271 Patented Feb. 19, 11963 wherein R is an aliphatic hydrocarbonbridge, each n independently has one of the values 0 and 1, and X is analkyl radical containing from 1 to 4 carbon atoms.

The compounds having two oxirane rings and employed for combination withthe reactive amine, such as triethanolamine, are characterized by thefollowing formula and cogenerically associated compounds formed in theirprepin which R represents a divalent radical selected from the class ofketone residues formed by the elimination of the ketonic oxygen atom andaldehyde residues obtained by the elimination of the aldehydic-oxygenatom, the divalent radical n H C. .C. H H

the divalent radical, the divalent sulfone radical, and the divalentmonosulfide radical -S, the divalent radical and the divalent disulfid-eradical S--S-; and R 0 is the divalent radical obtained by theelimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom fromthe phenol RI! I in which R, R", and R' represent hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent memberhaving not over 16 carbon atoms; n represents an integer including zeroand 1, and n' represents a whole number not greater than 3. Theabove-mentioned compounds and those cogenerically associated compoundsformed in their preparation are thermoplastic and organicsolvent-soluble. Reference to being thermoplastic characterizes productsas being liquids at ordinary temperature or readily convertible toliquids by merely heating below the point of pyrolysis and thusdifferentiates them from infusible resins. Reference to being soluble inan organic solvent means any of the usual organic solvents, such asalcohols, ketones, esters, ethers, mixed solvents, etc. Reference tosolubility is merely to differentiate from a reactant which is notsoluble and might be not only insoluble but also infusible. Furthermore,solubility is a factor insofar that it is sometimes desirable to dilutethe compound containing the epoxy rings before reacting with amine. Insuch instances, of course, the solvent selected would have to be onewhich is not susceptible to oxyalkylation, as for example, kerosene,benzene, toluene, dioxane,

various ketones, chlorinated solvents, dibutyl ether, dihexyl ether,ethyleneglycol diethylether, diethyleneglycol diethylether, anddimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The1,2-epoxy ring is sometimes referred to as the oxirane ring todistinguish it from other epoxy rings. Hereinafter the word epoxy unlessindicated otherwise, will be used to mean the oxirane ring, i.e., the1,2-epoxy ring. Furthermore, where a compound has two or more oxiranerings will be referred to as polyepoxides. They usually represent, ofcourse, l',2-epoxide rings or oxirane rings in the alpha-omega position.This is a departure, of course, from the standpoint of strictly formalnomenclature as in the example of the simplest diepoxide which containsat least 4-carbon atoms and is formally described asl,2-epoxy-3,4-epoxybutane (1,2,3,4 diepoxybutane).

It well may be that even though the previously suggested formularepresents the principal component, or compounds, of the resultant orreaction product described in the previous text, it may be important tonote that somewhat similar compounds, generally of much higher molecularweight, have been described as complex resinous epoxides which arepolyether derivatives of polyhydric phenols containing an average ofmore than one epoxide group per molecule and free from functional groupsother than epoxide and hydroxyl groups. See U.S. Patent No. 2,494,295,dated January 10, 1950, to Greenlee. The compounds here included arelimited to the monomers or the low molal members of such series andgenerally contain two epoxide rings per molecule and may be entirelyfree from a hydroxyl group. This is important because the instantinvention is directed towards products which are not resins and havecertain solubility characteristics not inherent in resins.

Having obtained a reactant having generally 2 epoxy rings as depicted inthe last formula preceding, or low molal polymers thereof, it becomesobvious the reaction can take place with any one of a number ofmono-amines or poly-amines which are oxyalkylation-susceptible. There isavailable considerable literature, particularly patent literature,dealing with oxyalkylation-susceptible amines or simple derivativesthereof, such as the esters of hydroxylated amines, for instance, higherfatty acid esters of triethanolamine and the like. Reference is made tosuch literature for a list of a large number of suitable reactants whichdo not require detailed description, although a rather comprehensivenumber of examples appear subsequently.

To illustrate the products which represent the subject matter of thepresent invention reference will be made to a reaction involving a moleof the oxylkylating agent, i.e., the compound having two oxirane ringsand triethanolamine. Proceeding with the example previously described itis obvious the reaction ratio of two moles of the amine to one mole ofthe oxyalkylating agent gives a product which may be indicated asfollows:

groups present, whether one or more, may or may not be significantlybasic and it is immaterial whether aqueous solubility represents theanhydro base or the free base (combination with water) or a salt formsuch as the acetate, chloride, etc. The purpose in this instance is todifferentiate from insoluble resinous materials, particular- 7 ture andare at least self-dispersing, and in many instances This is particularly true when there happens to be one or more nitro-' gen atomspresent or a repetitious ether'likage as in the Water-soluble, in fact,colloidally soluble.

case of oxyethylated or oxypropylated monoamines or polyamines.

For reasons which are obvious, the intermediate prodnot isoxyalkyla-tion-susceptible. It goes without saying that the final stepin the process of manufacture is nothing more nor less than reacting anyof the products obtained from the nitrogen-containing reactants, withethylene oxide, propylene oxide, butylene oxide, or the like.

Similarily, the products derived by oxyalkylation with a monoepoxide canbe subjected to further reaction with a product having both a nitrogengroup and a 1,2-epoxy group such as 3-dialkylaminoepoxypropane. See U.S.Patent No. 2,520,093, dated August 22, 1950, to Gross.

The new products are useful as wetting, detergent and leveling agents inthe laundry, textile and dyeing industries; as wetting agents anddetergents in the acid washing of building stone and brick; as wettingagents and spreaders in the application of asphalt in road building andthe like; as a flotation reagent in the flotation separation of variousaqueous suspensions containing negatively charged particles, such assewage, coal washing waste water, and various trade wastes and the like;as germicides, insecticides, emulsifying agents, as, for example, forcosmetics spray oils, water-repellent textile finishes; as lubricants,etc.

In the present instance the various condensation products as such or inthe form of the free base or in the form of the acetate, may notnecessarily be xylene-soluble although they are in many instances. Ifsuch compounds are not xylene-soluble the obvious chemical equivalent orequivalent chemical test can be made by simply using some suitablesolvent, preferably a water-soluble solvent such as ethylene glycoldiethylether, or a low molal alcohol, or a mixture to dissolve theappropriate product being examined and then mix with the equal weight ofxylene, followed by addition of water. Such test is obviously the samefor the reason that there will be two phases on vigorour shaking andsurface activity makes its presence manifest. It is understood thereference in in which the Various characteristics have their priorsignificance. However, molal ratios may be varied as noted subsequently.The product thus obtained was reacted further with monoepoxide asdescribed elsewhere.

Such intermediate product as above noted (prior to oxyalkylation with amonoepoxide) must, in turn also be soluble but solubility is not limitedto an organic solvent but may include water or, for that matter, asolution of water containing an acid such as hydrochloric acid, aceticthe hereto appended claims as to the use of xylene in the emulsificationtest includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided intoeight parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide andparticularly the diexpoxide reactant; Part2 is concerned with certaintheoretical aspects of acid, hydroxyacetic acid, etc; In other Words,the nitrogen diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation of monomericdiepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molalpolymeric epoxides or mixtures containing low molal polymeric epoxidesas well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolicreactants suitable for diepoxide preparation;

Part 4 is concerned with suitable nitrogen-containing compounds to beemployed for reaction with the polyepoxides;

Part 5 is concerned with the reactions involving the two preceding typesof materials and examples obtained by such reactions;

Part 6 is concerned with reactions involving the intermediates obtainedin the manner described in Part 5, preceding, and certain alpha-betamonoepoxides having not over 4 carbon atoms;

Part 7 is concerned with the resolution of petroleum emulsions of thewater-in-o-il type by means of the previous described chemical compoundsor reaction products; and

Part 8 is concerned with uses for the products herein described, eitheras such or after modification, including any applications other thanthose involving resolution or petroleum emulsions of the water-in-oiltype.

PART 1 As will be pointed out subsequently, the preparation ofpolyepoxides may include the formation of a small amount of materialhaving more than two epoxide groups per molecule. If such compounds areformed they are perfectly suitable except to the extent they may tend toproduce ultimate reaction products which are not solventsoluble liquidsor low-melting solids. Indeed, they tend to form thermosetting resins orinsoluble materials. Thus, the specific objective by and large is toproduce diepoxides as free as possible from any monoepoxides and as freeas possible from polyepoxides in which there are more than two epoxidegroups per molecule. Thus, for practical purposes what is saidhereinafter is largely limited to polyepoxides in the form ofdiepoxides.

As has been pointed out previously one of the reactants employed is adiepoxide reactant. It is generally obtained from phenol(hydroxybenzene) or substituted phenol. The ordinary or conventionalmanufacture of the epoxides usually results in the formation of aco-gcneric mixture as explained subsequently. Preparation of the monomeror separation of the monomer from the remaining mass of the co-genericmixture is usually expensive. If monomers were available commercially ata low cost, or if they could be prepared without added expense forseparation, our preference would be to use the monomer. Certain monomershave been prepared and described in the literature and will be referredto subsequently. However, from a practical standpoint one must weigh theadvantage, if any, that the monomer has over other low molal polymersfrom a cost standpoint; thus, we have found that one might as wellattempt to prepare a monomer and fully recognize that there may bepresent, and probably invariably are present, other low rnolal polymersin comparatively small amounts. Thus, the materials which are most aptto be used for practical reasons are either monomers with some smallamounts of polymers present or mixtures which have a substantial amountof polymers present. Indeed, the mixture can be prepared free frommonomers and still be satisfactory. Briefly, then, our preference is touse the monomer or the monomer with the minimum amount of higherpolymers.

It has been pointed out previously that the phenolic nuclei in theepoxide reactant may be directly united, or united through a variety ofdivalent radicals. Actually, it is our preference to use those which arecommercially available and for most practical purposes it meansinstances Where the phenolic nuclei are either united directly withoutany intervening linking radical, or else united by a ketone residue orformaldehyde residue. The commercial bis-phenols available now in theopen market illustrate one class. The diphenyl derivatives illustrate asecond class, and the materials obtained by reacting substitutedmonofunctional phenols with an aldehyde illustrate the third class. Allthe various known classes may be used but our preference rests withthese classes due to their availability and ease of preparation, andalso due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way,as pointed out elsewhere, our preference is to produce them by means ofthe epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains onlya modest amount of polymers corresponds to the derivative of bis-phenolA. It can be used as such, or the monomer can be separated by an addedstep which involves additional expense. This compound of the followingstructure is preferred as the epoxide reactant and will be used forillustration repeatedly with the full understanding that any of theother epoxides described are equally satisfactory, or that the higherpolymers are satisfactory, or that mixtures of the monomer and higherpolymers are satisfactory. The formula for this compound is Referencehas just been made to bis-phenol A and a suitable epoxide derivedtherefrom. Bis-phenol A is dihydroxy-diphenyldimethyl methane, with the4,4-isomers predominating and with lesser quantities of the 2,2 and 4,2isomers being present. It is immaterial which one of these isomers isused and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, towit, Part 1, and in succeeding parts, the text is concerned almostentirely with epoxides in which there is no bridging radical or thebridging radical is derived from an aldehyde or a ketone. It would beimmaterial if the divalent linking radical would be derived from theother groups illustrated for the reason that nothing more than meresubstitution of one compound for the other would be required. Thus, whatis said hereinafter, although directed to one class or a few classes,applies with equal force and effect to the other classes of epoxidereactants.

If sulfur-containing compounds are prepared they should be freed fromimpurities with considerable care for the reason that any time that alow-molal sulfur-containing compound can react with epichlorohydrinthere may be formed a by-product in which the chlorine happened to beparticularly reactive and may represent a product, or a mixture ofproducts, which would be unusually toxic, even though in comparativelysmall concentration.

PART 2 The polyepoxides and particularly the diepoxides can be derivedby more than one method as, for example, the use of epichlorohydrin 0rglycerol dichlorohydrin. If a product such as bis-phenol A is employedthe ultimate compound in monomeric form employed as a reactant in thepresent invention has the following structure:

Treatment with epichlorohydrin, for example, does not yield this productinitially but there is an intermediate produced which can be indicatedby the following structure:

H H n 61 ()H H (EH3 OH A71 Treatment with alkali, of course, forms theepoxy ring. A number of problems are involved in attempting to producethis compound free from cogeneric materials of related composition. Thedifficulty stems from a number of sources and a few of the moreimportant ones are as follows:

(1) The closing of the epoxy ring involves the use of caustic soda orthe like which, in turn, is an eifective catalyst in causing the ring toopen in an oxyalkylation reaction.

Actually, what may happen for any one of a number of reasons is that oneobtains a product in which there is only one epoxide ring and there may,as a matter of fact, be more than one hydroxyl radical as illustrated bythe following compounds:

(2) Even if ones starts with the reactants in the preferred ratio, towit, two parts of epichlorohydrin to one part of bis-phenol A, they donot necessarily so react and as a result one may obtain products inwhich more than two epichlorohydrin residues become attached to a singlebis-phenol A nucleus by virtue of'the reactive hydroxyls present whichenter into oxyalkylation reactions rather than ring closure reactions.

(3) As is well known, ethylene oxide in the presence of alkali, and forthat matter in the complete absence of water, forms cyclic polymers.Indeed, ethylene oxide can produce a solid polymer. This same reactioncan, and at times apparently does, take place in connection withcompounds having one, or in the present instance, two substitutedoxirane rings, i.e., substituted 1,2 epoxy rings. Thus, in many ways itis easier to produce 2.

polymer, particularly a mixture of the monomer, dimer and trimer, thanit is to produce the monomer alone.

(4) As has been pointed out previously, monoepoxides may be present and,indeed, are almost invariably and inevitably present when one attemptsto produce polyepoxides, and particularly diepoxides. The reason is theone which has been indicated previously, together with the fact that inthe ordinary course of reaction a diepoxide, such as I a chlorine atompresent.

7 drin.

8 spond in every respect except that one terminal epoxide group isabsent and in its place is a group having one chlorine atom and onehydroxyl group, or else two hydroxyl groups, or an unreacted phenolicring.

(5) Some reference has been made to the presence of a chlorine atom andalthough all effort is directed towards the elimination of anychlorinecontaining molecule yet it is apparent that this is often anideal approach rather than a practical possibility. Indeed, the samesort of reactants are sometimes employed to obtain products in whichintentionally there is both an epoxide group and See US. Patent No.2,581,464, dated January 8, 1952, to Zech.

What has been said in regard to the theoretical aspect is, of course,closely related to the actual method of preparation which is discussedin greater detail in Part 3, particularly sub-divisions A and B. Therecan be no clear line between the theoretical aspect and actualpreparative steps. However, in order to summarize or illustrate what hasbeen said in Part 1, immediately preceding reference will be made to atypical example which already has been employed for purpose ofillustration. The particular example is OH, H H H H H H O (1H3 0 It isobvious that two moles of such material combine readily with one mole ofbis-phenol A,

Jim

to produce the product which is one step further along, at least,towards polymerization. In other words, one prior example shows thereaction product obtained from one mole of the bisphenol A and two molesof epichlorohy- This product in turn would represent three moles ofbisphenol A and four moles of epichlorohydrin.

For purpose of brevity, without going any further, the next formula isin essence one which, perhaps in an idealized way, establishes thecomposition of resinous products available under the name of Epon Resinsas now sold in the open market. See, also, chemical pamphlet entitledEpon Surface-Coating Resins, Shell Chemical Corporation, New York City.The word Epon is a registered trademark of the Shell ChemicalCorporation.

on, on on,

has 1. on, nn

'or constituents. These materials may vary from simple non-resinous tocomplex resinous epoxides which are polyether derivatives of polyhydricphenols containing an average of more thanone epoxide group per moleculeand free from functional groups other than epoxide and hydroxyl groups.

Referring now to what has been said previously, to wit, compounds havingboth an epoxy ring or the equiv- 9, alent and also a hydroxyl group, oneneed go no further than to consider the reaction product of andbisphenol A in a mole-for-mole ratio, since the initial reactant wouldyield a product having an unreacted epoxy ring and two reactive hydroxylradicals. Referring again to a previous formula, consider an examplewhere two moles of bisphenol A have been reacted with 3 moles ofepichlorohydrin. The simplest compound formed would be thus:

CH2 Such a compound is comparable to other compounds having both thehydroxyl and epoxy ring such as 9,10- epoxy octadecanol. The ease withwhich this type of compound polymerizes is pointed out by U.S. PatentNo. 2,457,329, dated December 28, 1948, to Swern et al.

The same difliculty which involves the tendency to polymerize on thepart of compounds having a reactive ring and a hydroxyl radical may beillustrated by compounds where, instead of the oxirane ring (1,2-epoxyring) there is present a 1,3-epoxy ring. Such compounds are derivativesof trimethylene oxide rather than ethylene oxide. See U.S. Patents Nos.2,462,047 and 2,462,048, both dated February 15, 1949, to Wyler.

in which R, R", R' represent a member of the class consisting ofhydrogen and hydrocarbon substituents of the aromatic nucleus, saidsubstituent member having not I H3 (EH (3 3 Ha 5 3 Hi CHz over 18 carbonatoms; n represents an integer selected from the class of zero and 1,and n represents a whole number not greater than 3.

PART 3 Subdivision A The preparations of the diepoxy derivatives of thediphenols, which are sometimes referred to as diglycidyl ethers, havebeen described in a number of patents. For convenience, reference willbe made to two only, to wit, U.S. Patent 2,506,486, and U.S. Patent No.2,530,353.

Purely by way of illustration, the following diepoxides, or diglycidylethers as they are sometimes termed, are

exljfinse of repetition of What pp P included for purpose ofillustration. These particular vrously, it may be Well to recall thatthese materials may Compounds are d ib d i th t t t j t vary from simplesoluble non-resinous to complex nontioned.

TABLEI Ex- Patent ample Diphenol Diglycldyl ether refernumber enceCH2(C8H4OH)2 Di(epoxypropoxyphenyl)methaue 2,506 486 OH3CH(O ;H,OH)2..Di(epoxypropoxyphenyl)methylmethane. 2, 5061486 (OH3)2C(C6H40H)2-Dr(epoxypropoxyphenyl)dimethylmethan 2, 506,486 C2H C(OH3)(C0H4OH)2 D(epoxypropoxyphenyl)ethylmthylrnethane. 2, 506,486 (C2165): BELOHhDi(epoxypropoxyphenyl)diethylmethaue 2,506,486 GH3C(C3HT)(GBH4OH)2--Dr(epoxypropoxyphenyl)methylpropylmethane 2. 506,486 3C(C6H5)(CfiH-1OH)ZD (epoxypropoxyphenyl)methylphenylrnethane 2,506,486 C2HsC(CsH5)(OeH OHD (epoxypropoxyphenyl)ethylphenylmethaue 2,506,486 3H7C(CaH5)(CeH4 H)D1(epoxypropoxyphenyl)Eropylphenylmethane. 2,506,486 C4HQC( 6H5)(C&H40Dl(epoxypropoxyphenyl) utylphenylmethane 2, 506, 486 (CHaCaHOCH(CsH4OH)2Dr(epoxypropoxyphenyl)tolylmethane 2,506,486 (QH3COH4)C(CHJ)(CtiH4OH)2--- D1(epoxypropoxyphenyl)tolylmethyltuethane 2, 506.486Dlhydroxy diphenyl 4,4-b1s(2,3-opoxypropoxy)diphenyl 2, 530,353(OH3)O(C4H5-CBH3OH)2 2,2-bis(4-(2,3-epoxypropoxy)Z-tertiarybutylphenyDpropane..- 2, 0,353

RI! RI or for greater simplicity the formula could be restated thus:

H H2 H2 $15 Ha Subdivision B As to the preparation of low-molalpolymeric epoxides or mixtures reference is made to numerous patents andparticularly U.S. Patents Nos. 2,575,558 and 2,582,985.

To the extent that one can propose a formula, even though it is anover-simplified idealization, it appears extremely desirable to includespecific reference to aforementioned US, Patent No. 2,575,558. Thereason is that this patent includes the same formula which has beenreferred to previously in Part 2, which is concerned with thetheoretical aspects of diepoxide preparation. Furthermore, this formula,or its counterpart, appears in the hereto appended claims.

TABLE II C-CC- OR -[R]nR OO-CC -OR -[R],,R1OO-CC Hg H H2 Ha I Ha H: H H;

(in which the characters have their previous significance) Example R O-from HR OH -R n 'n Remarks number B1 Hydroxy benzene CH3 1 0,1,2 Phenolknown as bis-phenol A. Low polymeric mixture about A; or more Where n=0,remainder largely where 'n=l, some where n=2. z

132 do CH3 1 0, 1, 2 Phenol known as bis-phenol B. See note regarding B1above.

B3 Orthobutylphenol CH 1 0,1, 2 Even though 'n is preferably 0, yet theusual reaction product might well con- -C tain materials where n is 1,or to a lesser degree 2. Ha

B4 Orthoamylphenol (IJH; 1 0,1,2 Do.

B5 Orthooctylphenol CH| 1 0,1,2 Do.

I CH:

136 Orthononylphenol (3H3 1 0,1,2 Do.

CHa

B7 Orthododecylphenol (3113 1 0,1,2 Do.

(|j V CHa B8 Metaeresol CH 1 0,1,2 See prior note. This phenol used as Iinitial material is known as bis-phenol -G O. For othersuitable'bis-phenols see I U. S. Patent 2,564,191. CH:

B9 do (311; 1 0, 1, 2 See prior note.

(i'). (3H2 CH3 B10 Dibutyl (orthc-para) phenol. 1% 1 0,1,2 Do.

1311..... Diamyl (ortho-para) phenol. 1g 1 0,1,2 Do.

1312 Dioctyl (ortho-para) phenol. I5 1 0,1,2 Do.

B13 Dlnonyl (ortho-para) phenol. 1g 1 0, 1, 2 Do.

B14 Diamyl (ortho-para) phenol. 7 I01 1 0, 1,2 Do.

I CH3 B15 "do H 1 0, 1, 2 Do.

CZHB

B16 Hydroxy benzene"; i (I) 1 0,1,2 D0.

B17 Dlamyl phenol (ortho-para). -s-s- '1 0,1,2 Do.

B18 -d0 -S- 1 0, 1, 2 Do.

TABLE II-Continued Example R1O- from HRlOH R n n Remarks number B19Dibutyl phenol (ortho-para). g 1% 1 0,1,2 Do.

B20 do H H 1 0,1,2 Do.

B21 Dinonylphenol(ortho-para). 1g 1 0,1,2 Do.

B22 Hydroxy benzene (6 1 0,1,2 Do.

B do None 0 0,1,2 Do.

B24 Ortho-isopropyl phenol CH3 1 0,1,2 See priornote. (As topreparationof 4,4- isopropylidene bis-(2-isopropylphonel) -O see U. S.Patent No. 2,482,748, dated 1 Sept. 27, 1949, to Dietzler.) CH3 B25Para-oetyl phenol CHzS-CH2 1 0,1,2 See prior note. (As to preparation ofthe phenol sulfide see U. S. Patent No. 2,488,134, dated Nov. 15, 1949,to Mikeska et a1.)

B26 Hydroxy benzene CH3 1 0,1,2 See prior note. (As to preparation ofthe l phenol sulfide see U. S. Patent No. (]3- 2,526,545.)

(1H2 i C2H5 Subdivision C The prior examples have been limited largelyto those in which there is no divalent linking radical, as in the caseof diphenyl compounds, or where the linking radical is derived from aketone or aldehyde, particularly a ketone. Needless to say, the sameprocedure is employed in converting diphenyl into a diglycidyl etherregardless of the 'nature of the bond between the two phenolic nuclei.For

purpose of illustration attention is directed to numerous otherdiphenols which can be readily converted to a suitable polyepoxide, andparticularly diepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and thesubstituent group in turn may be a cyclic group such as the phenyl groupor cyclohexyl group as in the instance of cyclohexylphenol orphenylphenol. Such substitutents are usually in the ortho position andmay be illustrated by a phenol of the following composition:

CH H

wherein R is a substituent selected fromthe class consisting ofsecondary butyl and tertiary butyl groups and R is a substituentselected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl,and alkaryl groups, and wherein said alkyl group contains at least 3carbon atoms. See US. Patent No. 2,515,907.

in which the -C H groups are secondary amyl groups. See U.S. Patent No.2,504,064.

CoHm e is See US. Patent No. 2,285,563.

See U.S. Patent No. 2,503,196.

wherein R is a member of the group consisting of alkyl, and alkox-yalkylradicals containing from 1 to 5 carbon See U.S. Patent No. 2,331,448.

r5 atoms, inclusive, and aryl and chloraryl radicals of the benzeneseries. See U.S. Patent No. 2,526,545.

CH=CH OH OH I C=CH HsC- CH See U.S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

OH OH As to descriptions of various suitable phenol sulfides, referenceis made to the following patents: U.S. Patents Nos. 2,246,321,2,207,719, 2,174,248, 2,139,766, 2,244; 021, and 2,195,539.

As to sulfones, see U.S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or someother aldehyde, particularly compounds such as Alkyl Alkyl Alkyl R5Alkyl invention:

OH on; 0H 0H Rn R R1 R2 in which R and R are alkyl groups, the sum ofwhose carbon atoms equals 6 to about 20, and R and R each preferablycontain 3 to about carbon atoms, and x is 1 to 4. The term sulfides asused in this text, therefore, includes monosulfide, disulfide, andpolysulfides.

As previously noted, Part 4 is concerned with the amino reactantsemployed in conjunction with the polyepoxide reactant usually containingtwo oxirane rings. Since the reactant described in detail in Part 3,preceding, is essentially an oxyalkylating agent it is obvious that anyamino compound, and more broadly any nitrogen-containing compound suchas an amide, which is oxyalkylation susconjunction with any alcohol orphenol.

ceptible is suitable for the present purpose. In essence, this meansthat the product must have a labile hydrogen attached to either oxygenor nitrogen. Such hydrogen atom may be attached directly to a nitrogenatom as in the case of an amide, an amine, or the like. However, it maybe attached directly to oxygen as in the case of triethanolamine; or alabile hydrogen atom in the form of a hydroxyl group may appear in theacyl radical of an amide or the ester of an amine, such as an ester ofethanoldiethyl amine; although ricinoleic acid exemplifies an acylradical with a hydroxyl group which is somewhat reactive, yet moresatisfactory, is a hydroxy carboxylic acid such as 1 wherein R is asix-sided carbocycle of the formula C H as described in U.S. Patent No.2,457,640, dated December 28, 1948, to Bruson et a1.

One need not necessarily use monoamino compounds or compounds containinga single nitrogen atom but may use polyamino compounds including, ofcourse, .compounds where there is more than one amide group. There is nolimitation as to the group which is attached to the nitrogen atominsofar that it may be alkyl, aryl, alicyclic, and alkylaryl, arylalkyl,etc. Heterocyclic compounds such as morpholine may be employed. Theamino compound or amido compound may be water-soluble orWater-insoluble. The amine may contain a phenolic hydroxyl as, forexample,

CHzNH where R is an alkyl group generally having five carbon atoms ormore. See U.S. Patent No. 2,410,911, dated November 12, 1946, to Wassonet a1. Further examples appear in the subsequent text. 7

Needless to say, since it is specified that the amino compound or amidocompound be oxyalkylation susceptible it can be subjected to reactionwith some other alkylene oxide than the instant reactant containing thetwo oxirane rings, such as ethylene oxide, propylene oxide, butyleneoxide, styrene oxide, glycide, glycidyl ethers of methanol, ethanol,propanol, phenol, and the like. The fact that such reactants areoxyalkylation susceptible means they are also susceptible to reactionwith imines, such as ethyleneimine, propyleneimine, etc. Furthermore,any non-nitrogenous compound which is oxyalkylation susceptible, forinstance, an alcohol or a phenol, may be reacted with ethylene-imine togive suitable compounds to be employed as reactants in the presentprocedure. See, for example, U.S. Patent No. 2,318,729, dated May 11,1943, to Wilson. This same procedure, of course, described in saidWilson patent can be used in Indeed, watersoluble polymers of loweralkylene imines can be employed. See U.S. Patent No. 2,553,696, datedMay 22, 1951, to Wilson. The imines may have ether linkages aspreviously noted. See, for example, the products described in U.S.Patent No. 2,325,514, dated July 27, 1943, to Hester.

As is obvious from What is said, one need not use organic compounds butinorganic compounds such as ammonia or hydrazine can be employed. In thecase of amides, one is not limited to the amides of monocarboxy orpolycarboxy acids but one may usetsulfonamides or the amide of carbonicacid, i.e., urea. However, certain derivatives of urea appear moresatisfactory than urea itself. See U.S. Patent No. 2,352,552, dated June27, 1944, to Kienzle.

As to a variety of sulfonamides which are readily susceptible tooxyalkylation, particularly with ethylene oxide 17 or propylene oxide,see US. Patent No. 2,577,256, dated December 4, 1951, to Lundsted. Suchsulfonamide could be used as such or after treatment with one or moremoles of ethylene oxide, propylene oxide, etc.

For purpose of convenience attention is directed to a sizable number ofnitrogen-containing compounds which are available in the open market asdifferentiated from those which could be readily prepared by reactionwith ethylene oxide, propylene oxide, ethyleneimine, etc. In someinstances even these reactants, notwithstanding the fact that they dohave a labile hydrogen atom, are more satisfactory after treatment withethylene oxide so as to have the labile hydrogen atom attached to oxygeninstead of nitrogen.

Amine 220 (Carbide and Carbon Chemicals Company,

New York City, N.Y., designation for Amine 803 (Carbide and CarbonChemicals Company,

New York City, N.Y., designation for N-butyl diethanolamine Aminoethylethanolamine Di (Z-ethylhexyl) ethanol- Morpholine amine N-hydroxyethylTetraethanol ammonium morpholine hydroxide N-aminoethyl morpholineN-aminopropyl morpholine N-acetyl ethanolamine N,N-diethyl ethyleneMonoethanolamine diamine Diethanolamine MonoisopropanolamineTriethanolamine Diisopropanolamine N-methyl ethanolamineTriisopropanolamine Dimethyl ethanolamine Dimethyl isopropanol- N-ethylethanolamine amine N-ethyl diethanolamine N-methyl diethanolaminen-amylamine Di-n-amylamine sec-amylamine Dibutyl isopropanolaminel,3-diaminopropane S-diethylaminopropylamine 1,3-diaminobutaneHirxylamm? 1,3-bis-ethylaminobutane Dlhexylanjune N-ethylbutylamine'Heptyhmme 2-amino-4-methylpentane Otjiylamm? 4-amino-2-butanolDloctylahnme l-dimethylarnino-Z- Decylamme p r op a n 01 DodecylammeS-isopropylamino-l- Diethyl ethanolamine pentanol N-butylaniline Highmolecular weight aliphatic amides known as Armid 8, Armid l0, Armid 12,Armid 14, Armid 16, Armid l8, Armid HT, Armid RO, Armid T, Armid TO andArmid C, as described in a chemical pamphlet entitled Armids, issued byArmour Chemical Division, Chicago 9, Illinois.

Similarly, secondary high molecular weight aliphatic amines known asArmeen 2C and Armeen 2HT, as de- I8 scribed in circular entitledSecondary Armeens, as issued by Armour Chemical Division, Chicago,Illinois.

Also, high molecular weight aliphatic amines known as Armeen 10, Armeen16D, Armeen HTD, Armeen 18D, and Armeen CD, as described in a pamphletentitled Armeens, issued by Armour Chemical Division, Armour andCompany, Chicago, Illinois.

Included also are fatty diamines having both primary and secondary aminegroups and sold under the name Duomeens, such as Duomeen T, as describedin a circular entitled Duomeen T issued by Armour Chemical Division,Chicago, Illinois.

Other suitable amines are primary monoamines of the type I-I(OC H NHwhere 11:3 to 5.

Suitable amines having an aromatic ring include alphamethylbenzylarnine,alpha -methylbenzylmonoethanolamine and alpha-methylbenzyldiethanolamine.

One may use tertiary alkyl primary amines such as tertiary-octylamine,alkylamine 8l-R, alkylamine 81-T, alkylamine JM-R, and alkylamine IM-T.As to a description of these amines see Rohm & Haas Company,Philadelphia, Pa., pamphlet entitled Tertiary-Alkyl Primary Amines.

Other amines include:

Z-amino-Z-methyl-l-propanol Z-amino-Z-methyl-1,3-propanedio12-amino-2-ethyl-1,3-propanediol 3-amino-2-methyl-l-propanolZ-amino-l-butanol 3-amino-2,2-dimethyl-l-propanol2-amino-2,3-dimethyl-l-propanol 2,2diethyl-2-amino ethanol2,2-dirnethyl-2-amino ethanol 3-amino-l,2-butanediol4-amino-l,2-butanediol 2-amino-1,3-butanediol 4-amino-l,3-butanediol4,4-dimethyl-1,3-butanediol 2-amino-l,4-butanediol3-amino-l,4-butanediol 1-amino-2,3-butanediol Tris-(hydroxy methyl)amino methane An additional desirable group of amines aredialiphaticaminoalkylcardanols, and particularly those having 10 to 40carbon atoms in the dialiphatic grouping; examples includedi-Z-ethylhexylaminomethylcardanol, diamylaminomethyl cardanol,dilaurylaminomethyl cardanol, and di-n-butylaminomethyl cardanol. SeeUS. Patent No. 2,489,672, dated November 29, 1949, to Revukas.

Further examples of this same type of material and which has availableboth a phenolic hydroxyl and an alkanol hydroxyl is illustrated by thecondensation prod not derived from a phenol, either monofunctional ordifunctional, such as para-tertiary butylphenol, para-tertiaryamylphenol, octylphenol, nonylphenol, and similar phenols having asubstituent such as two butyl groups or two nonyl groups in both anortho and the para position. Such phenols are reacted with an aldehyde,such as formaldehyde, acetaldehyde, etc. and an alkanol phenol, such asdiethanolamine, ethylethanolamine, dipropanola- .rnine, and other amylamines having only one amino hydrogen atom. See, for example, US. PatentNo. 2,457,634; dated December 28, 1948, to Bond et al.

1 Amines having ring structures of course include aniline,diphenylamine, cyclohexylamine, dicyclohexylamine, and variouscomparable amines with alkyl substituents in the ring and similarly suchamines after treatment with ethylene oxide, propylene oxide, glycide,etc.

It is to be noted, of course, that the above description in the textimmediately preceding is largely miscellaneous in character because thereference is to products available in the open market. Practically everyamine which is oxyalkylation susceptible is also acylation susceptiblealthough there are some compounds, such as See footnotes at end oftable.

TABLE III-Continued Ex. Molar Time of Max. No. Reactants ratioreaiction, tv mo Color and physical state Solubility C15...N-amiuopropyl morpholine, 72 g. 221 7.5 126 Yellow sticky semi-solidH2O, insoluble; 5% acetic acid, soluble;

plus 3A 85 g. xylene, soluble. C16... N-hydroxggtgyl morpholine, 65.52:1 7.5 145 Dar}: brown sticky semi- Do.

is. p us 5 g. so O17--- Oyclohexylamine, 99 g. plus 3.4 2:1 9.5 142 Darkbrown semi-solid H20, insoluble; 5% acetic acid, dispersible;

170 g. xylene, soluble. O18.-- Dl-2-eti1ylhexyl ethanolamine, 2:1 24 200Brownish thick liquid D0.

142.5 g. plus 311 85 g. Cl9 Triethanolamine plus urea 1:4, 60 2:1 4 150Yellow hard solid H2O, insoluble; 5% acetic acid, insoluble;

plus 100 g., 3.4 68 g. xylene, insoluble; CHsOH, soluble. C20...Trietbanolamine plus propylene 2:1 2 150 Dark brown sticky mass H2O.insoluble; 5% acetic acid, soluble;

oxide 1:3, 161.5 g. plus 311 85 g. xyt'llene, insoluble; xylene+Ha0H,solu e. C21 Triethanolamine plus ethylene 2:1 2 150 Brownish red thickliquid..- H20, soluble; acetic acid, soluble; xylene,

oxide 1:3, 140.5 g. plus 3A 85 g. insoluble; xylene-l-CHaOH, soluble.C22.-. Triethanolamine plus ethylene 2:1 6.5 156 Dark brown thick liquidD0.

' oxide 1:6. 206.5 g. plus 3A 85 a. O23 Tricthanolamine plus propylene2:1 6. 5 157 .do H2O. insoluble; 5% acetic acid, soluble; oxide 1:6,248.5 g. plus 3A 85 g. xyllelgle. partly soluble; xylene plus 011 011,

so u e. C24 Triethanolainine plus ethylene 2:1 6.5 165 do H2O. soluble;5% acetic acid. soluble; xylene.

oxide 1:9, 272.5 g. plus 3A. 85 g. insoluble; xylene lus CHiOH. soluble.C25 'Iriethnnolarnine plus propylene 2:1 13 165 do H20. insoluble; 5%acetic acid, soluble; oxide 1:9. 268.4 g. plus 3.4 68 g. xylleglepartlysoluble; xylene plus CHaOH.

so u e. C26 2an1inopyridine, 94 g. plus 3.4 2:1 17 160 Black hard solidH20. insoluble; 5% acetic acid. soluble;

170 a. xylene. insoluble; OHIiOII, soluble. C27 N-methyl aniline. 53.5g. plus 3A 2:1 4 162 Amber-colored semi-solid.. H2O. insoluble; 5%acetic acid. insoluble;

85 2'. xylene, soluble. C28 N efitliylaniline. 60.6 g. plus 3A 2:1 4 157Brown semi-solid Do.

2. O29 Ethyl diethanolamine.68.5 g. plus 2:1 4 147 Brown rubbery massH20. insoluble; 5% acetic acid. soluble 3A 85g, (diflicult); xylene.soluble, partly; xylene plus CHsOH. soluble. C30 Butyldiethanoiamine,82.5 g. plus 2:1 4 163 Dark brown thick liquid H20.insoluble; 5% acetic acid. soluble; 3A 85 g. xyilelnie. partly soluble;xylene plus 0113011, S0 [1 e. 'O31 Benzylamine. 53.6 g. plus 3A 85 g..2:1 3 176 Yellow solid Hi0. insoluble; 5% acetic acid, disoersible;xyllegie. partly soluble; xylene plus CHaOH. so u e. C322-amino-4-methyl pentane, 50.5 g. 2:1 3 142 Brownish solid H10,insoluble; 5% acetic acid. dispersible;

plus 3A 85 g. xylene, soluble. C33 2-arnino-2-ethyl 1,3-propanediol, 2:18 154 Dark brown solid H2O, insoluble; 5% acetic acid, soluble; 66.5 g.plus 3A 85 g. xsilegle, insoluble; xylene plus CHzOH,

son 0. C34 2-amino-2-methyl l,3-propanecliol, 2:1 3 162 Brown solid H2O,insoluble; 5% acetic acid, soluble;

54.5 5. plus 3A 85 g. xylene insoluble; xylene plus CH OH, soluble(difficult). C35 Diamylamine, 78.7 g. plus 3A 85 2:1 6 170 Brownviscousliquid H2Oi insoluble}; 5% acetic acid, insoluble xy ene, SO L10. C36 Nonylalnine, 71.7 g. plus 3A 85 g 2:1 6 170 Yellow semi-solid Do.Q37 Di-12etl31yl85hexylamine, 120.5 g. 2:1 6 175 Yellow viscous liquidD0.

p us g. C38 Furfurylaminc, 97 g. plus 3A 170 g-. 2:1 6 170 Dark brownsemi-solid Hi0i insolulbllel; 5% acetic acid, dispersible;

' xy ene, so u l e. C39 Ethylenediamine, 60 g. plus 3A 2:1 2. 5 110Yellow semi-solid H2O. insoluble; 5% acetic acid, soluble; 170 g.xylleiia, insoluble; xylene plus 011 011,

so u a. C40 Prltgylene diamine, 74 g. plus 3A 2:1 2.5 112 -.do Do.

. 'C41 Pgiiiesrgylene diamine, 54 g. plus 2:1 162 Black brittle solidDo.

g. C42 Diethylene triamine, 103.2 g. plus 2:1 6 150 Brownish semi-solidH2O. dispersible; 5% acetic acid, soluble, 3A 170 g. xyllegle,dispersible; xylene plus CHaOH,

so u o. C43 Tetlraetshzlseie pentamine, 94.7 g. 2:1 4 150 Amb er-coloredsemi solid Do.

pus g. Q44 Tetraethanol tetraethylene penta- 2:1 4 145 Dark ambercolored semi- H2O, dispersible 5% acetic acid, soluble; mine 182.7 g.plus 3.4 85 g. solid. xyllege, dispersible; xylene plus CHaOH,

. so u .0. C45 Nitrogen compound, 141.6 g. plus 2:1 5.5 180 Dark brownbrittle solid H2O, insoluble; 5% acetic acid, soluble;

3A 51g. H xylene, soluble. C46; Nitioggn compound, 206 g. plus 2:1 5.583 Daflrlidamber colored thick Do.

g. I u C47 Triethanolamine plus Propylene 2:1 7 165 Dark brown thickliquid Do.

oxide 1:12, 169 g. plus 3A 34 g. (34s Triethanolamine plus ethylene 2:17 170 Dark brown thick liquid. H2O soluble; 5% acetic acid, soluble;xylene, oxide 1:12, 135.4 g. plus 3A 34 g. I I solullle (partly); xyleneplus CHGOII,

. so u e. C49 Trietbanolamine plus propylene 2:1 1.75 110 Yellow thickliquid. H2O, insoluble; 5% acetic acid, soluble;

oxide 1:18, 238.6 g. plus 3A 34g. xylene, soluble. C50 Triethanolamineplus ethylene 2:1 2. 5 160 Dark brown thick liquid H2O, soluble; 5%acetic acid, soluble; xylene, oxide 1:18, 188.2 g. plus 3.4 34 g.solulgle (cloudy); xylene plus CH3OH, so u e. 051;; Triethanolamine plusPropylene 2:1 2.5 H20, disporsiblc; 5% acetic acid, soluble; o\idc 1:15,203.8 g.plus3A 34 9. xylene, solulle. C52 TliEithinOllJIiinfi usethylene 2:1 2.5 H20, solutle; 5% acetic acid, soluble; xylene, oxide1:15, 161.8 g. plus 3A 34 soluble (cloudy); xylene plus CH OH,

sou e. e 053 Decylamine 10D, 78.5 g. plus 311 2:1 8.5 H20, insoluble; 5%acetic acid, insoluble;

85 g. xylene, soluble. C54 Dgciikegylamine 12D, 92.5 g. plus 2:1 8.5 Do.

. 5 l;- O55 fiefiiggcylamine 16D, 122 g. plus 2:1. 8.5 Do.

g. 056 Octgdeeylamino 18D, 133.5 g. plus 2:1 8. 5 Do.

3 g. C57 P-aminophenol, 54.5 g. plus 3A 2:1 8.0 H20, soluble; 5% aceticacid; soluble; xylene,

85 g. insoluble; xylene plus CH3OH, soluble. C58 Betarpheuylethyl amine,60.5 g. 2:1 8.0 Amber semisolid H2O, insoluble; 5% acetic acid,insoluble;

plus 3A 85 2. xylene, soluble. C59-.. Bcnzenesulionyl ethyl amide, 92.62:1 8.0 178 Amber thick liquid. Do.

a. plus 3A 85 g. C60--. Benzene sulfonyl isporopylamide, 2:1 8.0 do Do.

99.6 g. plus 3A 85 g.

Molar Time of Max. Ex. -Reactants ratio reactionv temp Color andphysical state Solubility No. (hrs) C.

(161.. Benzene sulfonarnide, 78.6 g. plus 2:1 7 2. 5 205 Dark brownsolid H2O, insoluble; 5% acetic acid, insoluble; 3A 85 g. xyllerlile,insoluble; xylene plus CHsOH,

. S 11 6. C62.-. P-toluene sulfonyl ethylamide. 2:1 2. 190 Amber thickliquid H1O, insoluble; 5% acetic acid, insoluble;

99.7 g. plus 3A 85 g. xylene, soluble.

C63.-. Armid 10,4 86 g. plus 311 85 g 2:1 8.0 170 Brown solid H1O,insoluble; 5% acetic acid, insoluble; xylene, insoluble; xylene plusCHaOH soluble.

C64- Armid 14, 57 g. plus 3A 43 g 2:1 8. 0 175 do Do.

G Armid 16, 64 5 g. plus 3A 43 g 211 8.0 100 Yellow solid... Do.

C66 Triethanolamine plus propylene 2:1 5.0 175 Dark brown liquid H2O,insoluble; 5% acetic acid, soluble;

oxide 12133.8 g. plus 3A 17 g. xylene, soluble.

C67--- Triethanolamine plus propylene 2:1 4. 5 180 do Do.

, oxide 1:27, 171.5 g. plus 311 17 g.

C68 'Iriethanolamine plus propylene 2:1 4. 5 185 .do Do.

oxide 1230.2, 190 g. plus 3A 17 g. C69-.- Triethanolamine plus ethylene2:1 4. 5 190 .do H1O, soluble; 5% acetic acid, soluble; xylene 1:212,108.2, g. plus plus alcohol, soluble.

C70--- Trietanolamine plus ethylene 2:1 4. 5 180 do H2O, soluble; 5%acetic acid, soluble; xylene oxide 1:24.21, 121.8 g. plus 3.4 17 g. plusalcohol (1:1 mix), soluble.

C71-.. Trietianolamine plus ethylene 2:1 4. 5 185 do Do.

oxide 1:26.9, 133.3 g. plus3A 17g.

C72--- Trietianolainine plus ethylene 2:1 4. 5 Do.

oxide 1:33.55, 163.6 g. plus 3A 17 g.

C73.-. Furlurylmnine plus propylene 2:1 2.0 H20, insoluble; 5% aceticacid, soluble;

ox1de1:17.9,113.5 g. plus 3A 17 g. xylene, soluble.

C74... Furfuryla nine plus propylene 2:1 2. 0 Do.

oxide 1:21, 131.5 g. plus 3A 17 g. C75. Furiurylamine plus propylene 2:12.0 Do.

oxide 1:24, 148.9 g. plus 3A 17 g. C76 Furlurylamine plus propylene 2:12. 0 Do.

oxide 1:26.5, 163.4 g. plus 3A 17 g. C77--. Furiurylarrine pluspropylene 2:1 1.0 Do.

oxide 1:305, 186.6 g. plus 3A 17 g. 078. Furiurylamine plus propylene2:1 1. 0 Do.

oxide 1:51.8, 155 g. plus 3.4 9 g. C79-.. 'Ietraethylene pentamine plus2:1 2 100 Dark brown thick liquid H20, dispersible; 5% acetic acid,soluble;

- propylene oxide 1124.3, 160 g. xylene, soluble. plus 3A 17 g. C80Diethylene triamine plus propyl- 2:1 0. 5 120 Brown thick liquid Do.

, gale oxide 1:9.8, 134.4 g. plus 3A g. 081. Diethylene triamine pluspropyl- 2:1 0.5 147 do Do.

one oxide 1118.7, 118.8 g. plus 3A l g. C82--- Triethylene tetramineplus pro- 2:1 0. 5 do Do.

p7 vlene oxide 1:12, 85.2 g. plus 3A l g. 083." Tricthylene tetramineplus pro- 2:1 0. 5 95 do Do.

pylenc oxide 1:19.6, 128.4 g. plus 3A 17 g. n

084... Propylene diamine plus propylene 2: 1 1 H2O, insoluble; 5% aceticacid, soluble; xylene oxide 1:8.5, 564g. plus 3A 17 g. soluble.

C85.-- Propylene diamine plus propylene 2:1 1 Do.

7 oxide 1:103, 67 g. plus 3A 17 g.

C86.-- Propylene diamine plus propylene 2: 1 1 Do.

oxide 1:20, 121 g. plus 3A 17 g.

C87-.- Propylene dia ine plus propylene 2:1 1 Do.

oxide 1:25, 183 4. plus 311 17 g.

C88.-- Meta-phenylene diamine plus 2:1. 1.5- 90 Dark amber thick liquidH1O, insoluble; 5% acetic acid, dispersible;

propylene oxide 1:1l.7, 78.6 g. xylene, soluble.

089... Meta-p enylene dlamine plus 2:1 2 do Do.

propylene oxide 1:27.6, 88.4 g. plus 3.4 9 g. C90 Meta-p enylene dlamineplus 2:1 2 .-.do Do.

52333710119 oxide 1:43, g. plus O91-" Meta-p enylene diamine plus 2:1 295 do Do.

' piAopylene oxide 1:55, 165 g. plus 7 3 9 g. -C92 Furfurylamine plus etylene ox- 2:1 .75 r 100 Brown thick liquid H 0, dispersible; 5% aceticacid, soluble ide plus propylene oxide 1:15.52 xylene, soluble. 11.3,143.4 g. plus 311 17 g. =C93 Furlurylamine plus et ylene ox- 2:1 .75 100do Do.

ide plus propylene oxide 1:155: v 16A. 173 g. plus 3A 17 g. 0940.Furfurylamine plus etylene ox- 2:1 2 do Do.

ide plus propylene oxide 1:15.5:

23.5, 214.2 1:. plus 3A-17 g. C95 Furfurylamine plus et ylene ox- 2:1. 2130 do Do.

' idc plus propylene oxide 1:155:

32.2, 264.7 g. plus 3A 17 g. C96.- Cationic amine 220, 15!) g. plus 3A2:1 8 200 Dark brown semi-solid H O, insoluble; 5% acetic acid, solublexylene, soluble.

1 2% sodium methylate used ascatalyst. Obtained by reaction from 2'molesbutylphenol, 2 moles formaldehyde, and 1 mole dihydroxyethyl,ethylenediamine. 3 Obtained by reaction-from 1 mole amylphenol resin, 2moles formaldehyde, and 2 moles diethanolamine.

4 See previous reference to this material.

5 Amine 220 is l-hydroxyet1yl-2-heptadecenyl glyoxalidine, a. product ofCarbide dz Carbon Chemicals Corporation.

N0'rE.--Produets obtained by oxyalkylation of amines, involving eitherox amine to alkylene oxide in this table and subsequent Table ofExamples.

yethylation'or oxypropylation, or both, are expressed in molal ratios ofAs previously pointed out one can use the product which is a mixture ofthe monomer derived from bisphenol A and corresponding to the previousformula of:

in which n varies from 1 to 3 oon2-i:-orr2 -o E Q a, Q,

and, as far as is possible to determine from molecular weight andhydroxyl value,

etc., it corresponds approximately to the following com- 15 position:

75 %-where n is 0 12%-where n is 1 8%where n is 2 5%where n is 3 Theaverage molecular weight is 460 compared to 340 for the monomer (where nis 0).

However, the fact that H3 1 be presence of some monoepoxide. In anyevent, a whole series of compounds has been made using this particularcogeneric mixture and assuming the molecular weight to be 462. The colorand physical appearance of the products were substantially the same asin the case of Table III. The xylene solubility was at least as good asthe corresponding compounds in Table III and the solu- Table III.Thedata bility in acetic acid was usually no better than, and perhapsnot quite as good as the corresponding products i is again summarizedfor convenienc in Table IV, following.

TABLE IV Ex. Molar Time of Max. No. Reactants ratio realgtion, tt mm,Color and physical state Solubility 1 Triethallolamine, 149-2 2 pl B1 12:1 7 6 142 brownish semi-solid H20, insoluble; 5% acetic acid, soluble231 g. 1 i i 5 xylene, soluble. 112.-.. Tiiig-isilp-opauolamlne, 94 g.plus 2:1 8. 5 183 --...do Do.

1 v E3. Dihydroxyethyl-ethylene di- 2:1 102 Brown semi-solid Do.

amine, 73 g. plus B1 116 g. j Y 134.--- Aniline, 93 g. plus B1 231g 2:15 94 Dark amber almost hard H2O, insoluble; 5% acetic acid, insoluble;solid. xyllegle, insolub e; xylene plus CHaOH,

. sou e. E5. Plgeiigrlethanolamine, 137 g. plus 2:1 4.5 93 Yellowbrittle solid Do. g. E6. Phenyldiethanolarnine, 90.5 g. 2:1 5 179 Darkamberi viscous liquid H2O, insoluble; 5% acetic acid, insoluble;

plus 131 116 g. p xylene, soluble. E7 Etl ylp lgen glethanolamine, 62.5g. 2:1 14 152 Amberliquid Do.

p us 1 g. E8. Diphenylamine, 84.6 g. plus B1 2:1 7 191 Brown liquid Do.

1 g. E9 Morpholine, 87 1;. plus B1 231 g 2:1 7 140 Amber solid mass Hi0iinsollllblltle; 5% acetic acid, soluble;

- 1 xy one, so u l e. E10 1,3-dimethyl urea, 88.1 g. plus 131 2:1 8.5202 Amber solid H2O, insoluble; 5% acetic acid, insoluble; 231 g.xylene. insoluble; CH OH, soluble. E11.-. 1,3diethy1 urea, 58.1 g. plusB1 2:1 5.5 181 Amber almost hard 1112155.... 1120, insoluble; 5% aceticacid, dispersiblo, 116 g. I xylene, soluble (hot). I 3 E12...Dibutylurea, 86 g. plus B1 116 g 2:1 5.5 172 Dark amber thick liquidH2Oi insolulblgi 5% acetic acid, dispersible,

, v r xyene,sou e. E13 Alpha-methylbenzyl ethanol- 2:1 7.5 155 Brownishalmost hard guess- Do.

amine, 82.5 g. plus Bl 116g. I E14... Alpha-methylbenzyl diethanol- 2:17. 5 150 Red thick liquid--- H2O, insoluble; 5% acetic acid, soluble;

- amine, 104.5 g; plus B1 116 g. I xylene, soluble. E15 NalminBopro%ylmorpholine, 72 g. 2:1 7. 5 129 Amber viscous liquid- Do.

p us 1 11 g. j 5 E16 N-hydroxyethyl morpholine, 65.5 2:1 7.5 .144 Amberviscous mass.-- Do.

g. plus B1 116 g. E17 Cyclohexylarnine, 99 g. plus B1 2:1 9.5 143 Brownalmost hard solid H2O, insoluble; 5% acetic acid, dispersible;

231 g. xylene, solu 6. E18 Di-2-ethylhexyl ethanolarnine, 2:1 2.4 202Brown viscous liquid Do.

142.5 g. plus B1 116 g. Y I v E19.-. Triethanolarnine plus urea 1:4, 2:14 148 Amber solid H2O, insoluble; 5% acetic acid, insoluble;

, plus g., plus B1 92.5 g. xylene, insoluble; CH3OH, soluble. E20Trietbanolarnine plus propylene 2:1 2 151 Brown viscous mass. H20,insoluble; 5% acetic acid, soluble; oxide 1:3, 161.5 g. plus B1 116 g.xyllegle, insoluble; xylene plus CHaOH,

' sou e. E21-" Triethanolamine plus ethylene 2:1 2 p 149 Reddish brownviscous H20, soluble; 5% acetic acid, soluble; xylene,

oxide 1:3. 140.5 g. plus B1 116 g. liquid. insoluble; xylene plus OHQOH,soluble. E22 Triethanolamine plus ethylene 2:1 6.5 158 Viscous brownliquid Do.

oxide 1:6, 2(l6.5 g. plus B1 116 g. I E23 Triethanolamine plus propylene2:1 6.5 do H20, insoluble; 5% acetic acid, soluble; oxide 1:6, 248.5 g.plus B1 116 g. xyllerela. partlysolublc; xylene plus OH3OH,

. sou e. E24" Triethanolarnine plus ethylene 2:1 6. 5 167 Brown viscousmass H O, soluble; 5% acetic acid, soluble; xylene,

oxyide 1:9, 272.5 g. plus B1 161 g. insoluble; xylene plus CHaOH,soluble. E25 Triethanolarnine plus prophylene 2:1 13 162 Thick brownliquid H2O, insoluble; 5% acetic acid, soluble; oxide 1:9, 268.4 g. plusB1 92.5 g. xyllefile, partly soluble; xylene plus CHsOH,

so no e. E26 2-Arninopyridine, 94 g. plus B1 2:1 17 158 Black hard massHi0, insoluble: 5% acetic acid, soluble;

231 g. xylene, insoluble; GHQOH, soluble. E27 N-methyl aniline, 53.5 g.plus Bl 2:1 4 165 Yellowish viscous liquid H2O, insoluble; 5% aceticacid, insoluble;

116 g. xylene, soluble. E28--- Nieltshyl aniline, 60.6 g. plus B1 2:1 4Brownish semi-solid Do.

E29.-- Ethyldiethanolamine, 68.5 g, plus 2:1 4 146 Brown viscous mass H0, insoluble; 5% acetic acid, ,soluble (dil- B1 116 g. ficult); xylene,partly soluble; xylene plus V CHQOH, soluble. E30---Butyldiethanolamine, 82.5 g. plus 2:1 4 160 Thick brown liquid H O,insoluble; 5% acetic acid, soluble; B1 116 g. xyllegiz, partly soluble;xylene plus CHsOH,

' S0 11 e. E31 Benzylamine, 53.6 g. plus B1 116 g. 2:] 3 178 Amber solidH2O, insoluble; 5% acetic acid, dispersible; xyllegle, partly soluble;xylene plus GH OH,

so u e. E32-.. 2-amino-4-methyl pentane, 505g. 2:1 3 143 .......do H O,insoluble; 5% acetic acid, dispersible;

plus B1 116 g. xylene, soluble.

See footnotes at end of table.

Ex. Molar Time of Max. N O. Reactants ratio reahction, te ux, Color andphysical state Solubility E33 2-amino-2-ethyl 1,3-propanedil, 2:1 3 152Dark amber solid 2O, insoluble; 5% acetic acid, soluble; 66.5 g. plus B1116 g. Xy1lG1Tl19, insoluble; xylene plus CH OH,

so no e. E34--- 2-amiuo-2-methyl 1,3-propanediol, 2:1 3 160 Amber solidDo.

54.5 g. plus B1 116 g. E35-.. Diamylaminc, 78.7 g. plus B1116 g. 2:1 6173 Amber thick liquid H2Oi insoluble; 5% acetic acid, insoluble;

xy one so u le. E36-.. Nonylarnine, 71.7 g. plus B1 116 gr. 2:1 6 169Amber viscous mass Do. E37". Di-l2-etl113ylhfgylarnine, 120.5 g. 2:1 6171 Amber thickliquid Do.

p us g. E38 Furfurylaminefl? g. plus 131 231 g 2:1 6 168 Dark amber massH2Oi insolulblg: 5% acetic acid, dispersible;

- xv one, so u le. E39--. Ethylene diainine, g. plus Bl 2:1 2. 5 112Amber viscous mass H2O, insoluble; 5% acetic acid, soluble; 231 g.xylleglc, insoluble; xylene plus CHQOH,

so u e. E40..- Pr2rrliyleue diaminc, 74 g. plus B1 2:1 2.5 114 do Do.

g. E41.-. p-ghclriglene diamine, 54 g. plus. 2:1 6 160 Dark brittlesolid Do.

1. E42-.. Diethylene trisminc, 103.2 g. plus. 2:1 6 173 Dark amber massH20, dispersible; 5% acetic acid, soluble; B1 231 g. xyllenf,dispersible; xylene plus GHQOH,

so u e. E43.-- Tet-methylene pentamine, 94.7 g. 2:1 4 151 Amber hardmass Do.

plus B1 116 g. E44--. Tetraethanol tetraethylene penta- 2:1 4 148Darkish brown almost hard Do.

mine, 182.7 g. plus B1 116 g. 7 mass. E45--. Nitrogen compound, 2 141.6g. plus 2:1 5. 5 176 'Dark amber bard mass .H O, insoluble; 5% aceticacid soluble;,

B1 6 g. xylene, soluble. E46--. Niriogsen compound, 206 g. plus 2:1 5.5V1scous yellow liquid Do. 7

4 g. E47. Triethanolamiue plus propylene 2:1 7 166 Viscous brown liquidDo. 7

- oxide 1:12, 169 g. plus B1 46 g. 7 E48... Triethanolamine plusethylene 011- 2:1 7 172 --.do H2O, soluble; 5% acetic acid, soluble; x ln ide 1:2, 135.4 g. plus B146 g. palrtgl soluble; xylene plus CHzOH,

so u e. E49 Triethanolamine plus propylene 2:1 1. 75 112 Viscous amberliquid H2O, insoluble; 5% acetic -.acid, soluble;

oxide 1:18, 2386 g. plus B1 46 g. xylene, soluble. E50.--Triethanolamine plus ethylene ox- 2:1 we 7 -2. '5 158 Dark amber viscousliquid-.- H O, soluble; 5% acetic acid, soluble; xylene, ide 1:18, 188.2g. plus B146 g. Y soluble but cloudy; xylene plus CH3OH, so u e. E51--.Triethanolamine plus propylene 2:1 2. 5 Dark amber thick liquid--- H2O,dispersible; 5% acetic acid, soluble;

oxide 1:15, 203.8 g. plus 131 46 g. V xylene, soluble. E52.-.Tricthanolamine plus ethylene ox- 2:1 2. 5 158 do..... H2O, soluble; 5%acetic acid, soluble; xylene, ide 1:15, 161.8 g. plus B146 g. solugle(cloudy); xylene plus CHaOH,

so u e. E53..- Dccylamine 10D, 78.5 g. plus B1 2:1 8.5 Amber mess H2O,insoluble; 5% acetic acid, insoluble;

115 g. xylene, soluble. E54-.. Dcgilecylamhie 12D, 92.5 g. plus 2:1 8.5186 do Do.

115 g. 4 E55... Heaxladecylamine 16D, 122 g. plus 2:1 8.5 172 -do Do.

115 g. E56 0%?de0yl8mllle 18D, 133.5 g. plus 2:1 8. 5 176 do Do.

115 g. E57 p-Aminophenol, 54.5 g. plus B1 2:1 8.0 173 Almost black solidH2O. soluble; 5% acetic acid. soluble; xylene,

' 115 g. insoluble; xylene plus CHQOH soluble. E58.-. Beta-phenylethylamme, 60.5 g. 2:1 8 150 Brownish viscous mass H2O, insoluble; 5%acetic acid, insoluble;

plus B1 115 g. I. xylene. soluble. E59 Benzene sullonyl ethylamide. 92.62:1 8 do Do.

g. plus B1 115 2. E60-.- Benzene sullonyl isopropylamide. 2:1 8 .173 -doDo.

' 99.6 g. plus B1115 g. I 7 E61". Benzene sulfonamide. 78.6 g. plus 2:12. 5 202 Dark brown solid mass Hi0. insoluble; 5% acetic acid,insoluble; 115 g. xyilelnie. insoluble; xylene plus CHsOH,

SO 11 e. E62..- p-Toluene sulfonylethyl amide. 2:1 2. 5 188 Yellowviscous-liqnid H O, insoluble; 5% acetic acid. insoluble;

, 99.7.g. plus B1 115 g. xylene. soluble. E63... Armid 10, 86 g. plus B1115 g 2:1 8.0 l 168 Dark amber mass H20. insoluble; 5% acetic acid.insoluble; xylene, insoluble; xylene plus GHaOH, V soluble. E64.-- Armid14. 57 g. plus B1 58 2' 2:1 8. 0 172 do D0. E65..- Arrnid 16; 64.5 g.plus B1 58 1!"... 2:1 I S. 0 189 Amber sol1d Do. E66--- Triethanolamineplus propylene 2:1 5. 0 172 Reddish brown liquid H O, insoluble; 5%acetic acid. soluble;

' oxide 1:20.5.133.8 3. plus B1 23 g. xylene, soluble. E67..-Triethanolamine plus propylene 2:1 4. 5 181 do Do,

oxide 1:27. 171.5 g. plus B1 23 .2. E68"; Ti-iethanolamine pluspropylene 2:1 4. 5 178 .clo Do.

oxide 1:302. g. plus B1 23 g. 7 E69 Triethanolarnine plus ethylene 2:1'4. 5 i 188 do HzO.S0lllble; 5% acetic-acid. soluble; xylene de 8.2 g.plus 131 23 8. plus alcohol; (1:1 mix). soluble. E70": Triethanolamineplus ethylene 2:1 4. 5 178 1o Do.

oxide 1:243, 121.8 g. plus B1 23 g. E71.-- Trlethanolamine plus ethylene2:1 4. 5 182 do Do.

oxide 1:26.9.133.3 2. plus B1 23 g. E72 Triethanolamine plus ethylene2:1 4. 5 183 do Do.

oxide 1:338, 163.6 g. plus B1 23 g. 3 E73 Furfurylamine plus propylene2:1 2.0 173 .do H2O, insoluble; 5% acetic acid. dispcrsiblc;

oxide 1:17.9. 113.5 grplus B1 23 g. xylene, soluble. E74--.Furfurylamine plus propylene ox-' 2:1 2.0 162 do Do.

ide 1:21. 131.5 g. plus B1 23 g. E75.-- Furiurylam'inc plus propyleneox- 2:1 2.0 178 do Do.

ide 1:24, 148.9 5:. plus 131 23 g. E76--- Furiurylamine plus propyleneox- 2:1 2.0 190 do Do. ide 1:265. 163.4 g. plus 151 23 g. 3377...Furfurylamine plus propylene ox- 2:1 1. 0 177 do Do.

' ide 1:30.5,186.6 g. plus B1 23 g. E78.-- Furiurylamine plus propylene2:1 1.0 182 Reddish liquid Do.

oxide 1:518, 155 g. plus B1 12.2 g.

l 2% soldium methylete used as catalyst. I

1 Obtained by reaction from 2 moles butylphenol, 2 moles formaldehyde,and 1 mole dihydroxyethyl, cthylenediannue.

3 Obtained by reaction from 1 mole am See'previous reference to thismaterial.

ylphenol resin, 2 moles formaldehyde, and 2 moles diethanolemine.

Previous attention has been directed to the fact that the diglycidylethers may not have any bridge connecting the aromatic nuclei, or thebridge may be derived from sulfur dichloride, from an aldehyde andparticularly formaldehyde, or may bethe residue of a sulfonic acid,i.e., a sulfone radical. There is no advantage in using these particularcompounds as far as we have been able to determine and thus ourpreference has been to employ compounds where the bridge is derived froma ketone and particularly acetone, due in part to commercialavailability. We have attempted to prepare comparatively viously notedand which appear for convenience again in Table V immediately following.The method of preparation, of course, is obvious in light of what hasbeen said previously, or what has been described elsewhere in theliterature.

As has been pointed out previously, our preference is to use compoundshaving at least one basic nitrogen and in many cases a repetitious etherlinkage obtained by oxyalkylation. The following derivatives wereobtained in the same manner as described previously in connection withdiglycidyl ethers where the bridge between the-phetechnically purecompounds corresponding to some prenolic nuclei happened to be, in mostcases, from a ketone.

TABLE V Ex. No.

H H H H /O\ F1--- mo o-oH o-crn-o-om H H H H 0 3H 0 (MW H H O l l H: CH2/GH H O 0 I t CH; CH: C2sHaiO4S (M.W.

(15 11 s' u I F3-.- H OH H sHn 1 1 CaHn CH: (3H2 /(iH /CH O l 0 l CH CHI 0x91143004 (M.W. 592) H H (u) H H F4 CH2OHCHzO-'-SC OCHg--OHCH:

II p 0 H H O H H 0 4 olsnwols (Mme) TABLE VI Ex. Molar Time of Max. No.Reactants ratio reahctiQ l, te m), Color and. physical state- SolubilityG1 Triethauolamine, 149.2 g. plus F1 2:1 6 Brown semisolid H2O,insoluble; 5% acetic acid, soluble; 149 g, f xylene, soluble. G2TrFi-isopropamola-mine, 94 g. plus 2:1 8 185 -do H201, sbolluble; 5%acetic acid, soluble; xylene,

"174.5g. sou e. 1 G3 Furiurylamine, 97 g. plus-Fl 149 g 2:1 6 180 Darkbrown semisolid H 0i insolulblgi 5% acetic acid, dispersiblc;

xy ene, so u e. Gt Tricthanolarnine plus ethylene ox- 2:1 2 Dark brownthick liquid H2O, soluble; 5% acetic acid, soluble; xylene, ide 1:18,188.2 g. plus F1 29.8 g. solugle (cloudy); Xylene plus CHaOH,

' 1 son G-5 Furturylarninc plus propylene ox- 2:1 2 170 -.do H2O,insoluble; 5% acetic acid, soluble;

, ide 1:17.9, 113.5 g. plus F1 14.9 g. xylene, soluble. G6Tricthanolamine, 74.6 g. plus F2 2:1 5 140 Dark semisolid Do.

, 117.5 g. G7 Tri-isopropanolamine, 94 g. plus 2:1 6 do Do.

2 7.5 g. G8 Furfuryl amine.97 g. plus F2 235 g. 221 6 do H2O, insoluble;5% acetic acid, dispersible; xylene. soluble. G9 Triethanolamine plusethylene 2:1 2 150 Dark thick liquid HaO.s0luble; 5% aceticacid,soluble; xylene, oxide 1:18,188.2 g. plus F247 g. solugle (cloudy);xylene plus CHaOH, S0 ll 8. G10 Furiurylamine plus propylene 2:1 2 165-do H2O. insoluble; 5% acetic acid, soluble;

'ggide 1:l7.9, 1135 g. plus F2 xylene,soluble. .5 a. G11Triethanolumine, 74.6 g. plus F3 2:1 3 140 Dark semisolid Do. 8g. 1312;,TrIi gsoigopauclamine, 94g. plus 2:1 3 150 do Do.

i 1 g. rG13 Furturylamine.97 g. plus F3 296 2:1 4 165 do H2O. insoluble;5% acetic acid. disperslble;

- Xylene. soluble. G14 Triethanolamine plus ethylene 2:1 2 150 Darkthickllquid H20, dsipersible; 5% acetic' acid, soluble;0xidel:18,188.2g. plus F3 59.2g. xylene, soluble (cloudy); xylene plus0H3OH,soluble. 1

TABLE VI-Continued Molar Time of Max. Ex. Reactants ratio reaction temp,Color and physical state Solubility No. (in-s.) 0.

G- Furfurylamine plus propylene 2:1 2 160 Dark thick liquidH3o.illS01l1b10; 5% acetic aeicLsoluble (hot);

ggile 1:17.59, 113.5 g. plus F3 xy1cne.soluble.

. g. G16--. Triethanolamine.149.2 g. plus F4 221 6 150 Dark semisolidH1O, insoluble; 5% acetic acid, soluble;

181 g. xy1eno,soluble. G17... Trll dsgiropanolamine, 94 g. plus 2:1 7180 do Do.

4 .5 g. G18-" Furl'ur-ylarnine, 97g. plus F4 181 g- 2:1 6 180 .'do H20iinsolulblgl; 5% acetic acid, dispersible;

xy one so u e. G19. Triethanolamine plus ethylene 2:1 2 160 Dark thickliquid H;O,soli1ble;5% acetic acid, soluble;xyl,ene,oxide1z18,188.2g.plusF436.2g soluile (cloudy); xylene plus GHKOH,

so u e. G20; Furfur-ylamine plus propylene 2:1 2 165 do H2O, insoluble;5% acetic acid, soluble;

oxide 1:17.9, 113.5 g. plus F4 18.1 xylene, soluble. g.

For reasons which are obvious in light of what has been said previously,the majority of examples, in fact all prior examples, are concerned withinstances where the ratio of the amine reactant to the polyepoxide istWo-to-one. One reason is that the epoxide is usually the most expensivereactant and, everything else being equal, one attempts to obtain thebest results with the least amount of the more, or most expensive,reactant. This ratio need not be employed. Other obvious ratios can beused; for instance, one may use a ratio of one-to-one, provided, ofcourse, that the amine preferably has at least two reactive hydrogenatoms. If the amine does not have at least two reacin dilute acid. Theyare also soluble or dispersible as a rule in xylene or a mixture ofxylene and methyl alcohol (one to-one). The products obtained werecomparatively thick liquids and indicated that the molecular size wasconsiderably higher in proportion than comparable. compounds obtained bythe two-to-one ratio. Such materials tend in the direction of potentialinsolubility and are particularlydesirable for the reason that theyadsorb rapidly at the interface. Likewise, when converted into newcompounds by oxyethylation, oxypropylation, acylation, or similarprocesses, the resultant of reaction has these same properties to anequal or greater degree.

TABLE VII Ex. Molar Time of Max. No. Reactants ratio reahction, te mm,Color and physical state Solubility H1 Triethanolamine plus propylene1:1 1.5 150 Yellow thick liquid H1O, insoluble; 5% acetic acid,dispersible; oxide 1:18, 119.3 g. plus 3A 34 g. xylene plus CHsOH,dispersiole. 112--.- Furfurylamine plus propylene ox- 1:1 1. 0 150 Brownthick liquid Do.

ide 1:51.8, 155 g. p us 3A 17 g. H3 Furfurylamine plus propylene ox- 1:1'2. 0 165 Yellow thick liquid Do.

ide 1266.8, 199 g. plus 3A 17 g. 114.... Furfurylamine plus ethylene ox-1:1 *2. 0 Dark liquid H2O, dlspersible; 5% acetic acid, soluble;

ide plus propyleneoxide 1:15.529, xylene plus CHQOH, soluble. 130 g.plus 3.4 84 g. 115...- Triet'iylenetetra'rinepluspropy- 1:1 1.0 Brownishthick liquid H1O, insoluble; 5% acetic acid, disperslole;

lene oxide 1: 12, 41.3 g. plus 3.4 17 xylene plus OH OH, soluble.

16.... Propylenediatnine plus propylene 1:1 1. 5 135 Yellow thick liquidDo.

, oxide 1210.3, 67 g. plus 311 34 g. 117-.-. Meta-phenylene dianine plus1:1 1. 5 120 Dark brown thick l1quid Do.

propylene oxide 1:27.6, 85.4 g. plus 3A 17 g. B8,.-. Diethylenctria'nine plus propy- 1:1 1.5 Brown thick liquid Do.

- lene oxide 1:18.7, 59.4 g. plus 3A 7 g. 119.... Furfurylaminepluscthylencoxlde 1:1 5 100' .----do H1O, dispersibie; 5% acetic acid,soluble;

plus propylene oxide 1:15.5:11.3, xylene, soluble. 143.4 g. plus 3.4 34g. H310." Furfurylarnine plusetiylene oxide 1:1 1 100 do Do. pluspropylene oxide 1:15.5:16.4, 173 g. plus 3A 34 g. H11 Furiurylarnineplusethyleneoxido 1:1 1 100 ..do Do,

' plus propylene oxide 1:15.5:28.5,

214.2 g. plus 311 34 g. a H12 Furiurylarnineplusethyleneoxide 1:1 1 100do Do.

plus propylene oxide 1:15.5:32.2, 264.6 g. plus 311 34 g.

tive hydrogen atoms, one mole of the epoxide may react PART 6 and makeavailable a new labile hydrogen atom wh1ch is then SUSCBptlblfi l0flllllhfl' reaction. on thfi other hand, 60 The preparanon of thecompounds or products deif the amine reactant has two or more labilehydrogen atoms then it becomes evident that one produces not only alinear type polymer but also that cross-linking may take place betweentwo linear polymers so as to produce an insoluble, or semi-insolublemass suggestive of -gelation or incipient thermosetting action, or onemay even obtain a hard type of resin suitable only for purposes otherthan those herein described and perhaps be useless for any purpose.

Note in the table following, i.e., Table VII, the materials obtained inthe manner described in this table use a molal ratio of one-to-one. Thereaction masses become semi-resinous and give solutions which usuallyare either scribed in Part 5, preceding, involves an oxyalkylatingagent, to wit, a olyepoxide and usually a diepoxide. The proceduredescribed in the present part is a further oxyalkylation step butinvolves the use of a monoepoxide or the equivalent. The principaldiflference is only that While polyepoxides are invariably nonvolatileand can be reacted under a condenser, at least numerous monoepoxides andparticularly ethylene oxide, propylene oxide, butylene oxide, etc.,involve somewhat different operating con ditions. Glycide andmethylglycide react under practically the same conditions as thepolyep-oxide. Actually, for purpose of convenience, it is most desirableto conduct the previous reaction, i.e., the one involving thepolyepoxide, in equipment such that subsequent reactionwithmonocxpoxides may follow without interruption. For this 33 reasonconsiderable is said in detail as to oxyethylation, etc. 7

As the oxyallzylation procedure is substantially conventional, andcarried out in equipment of the type commonly used for oxyalltylaticn,the procedure will simply be illustrated by the following examples:

Example H The oxyalk laden-susceptible compound employed was the resinpreviously described as Example El. Example El, in turn, was obtainedfrom triethanolamine and Example Bl as described in Table ii. Theautoclave employed in this particular instance was approximately 5gallons in size. in other instances somewhat larger autoclaves have beenused, for instance, 10, 25 or 35 gallon sizes. However, this isimmaterial. 8.5 pounds of oxyalltylatiomsuscepti le compound El wereplaced in the autoclave along with an equal amount of solvent. In thisseries of examples the solvent employed was xylene. This applies to theseries appearing in subsequent Table Vill with the exception that theseries derived from oxyallrylationsusceptible compound E3 used assolvent a 5 t) mixture of xylene and diethyleneglycol diethyl ether. Theamount of catalyst used (finely powdered caustic soda) was .8 pound.Adjustment was made to operate the autoclave at approximately 125 C. Insome other instances higher temperatures were employed, up to 130 C. or145 C. or 150 C. Adjustment was made also to operate at a pressure notin excess of 30 pounds per square inch. The time regulator was set so asto in iect 8.5 pounds of ethylene oxide slowly over a one-hour period.The reaction went readily and, as a matter of fact, the oxide was takenup probably in considerably less than this time. The speed of reaction,particularly at the comparatively low pressure, undoubtedly was due in alarge measure to effective agitation and also to the comparatively highconcentration of catalyst. The theoretical molecular weight at the endof the reaction was 1700. The molal ratio of ethylene oxide tooxyalkylation-susceptible compound (i.e., the initial resin) was 19.25to 1.

Example J2 This example illustrates further oxyalkylation of Example I1,preceding. The oxyalkylation-susceptible compound, to wit, E1, is thesame as was used in Example 31, because it was merely a continuation. Insubsequent examples, such as for example listed in Table VIII, theoxyalkylation-susceptible compound shown in the horizontal lineconcerned with Example I2 refers to oxyalkylation-susceptible compoundE1. Actually, one could refer just as properly to Example 11 at thisstage. It is immaterial which designation is used so long as its use ispracticed consistently throughout the tables. In any event, the amountof ethylene oxide used is the same as before, to wit, 8.5 pounds. Thismeans the oxide at the end was 17 pounds. Similarly, the ratio ofethylene oxide to oxyalkylation-susceptible compound (molar basis) atthe end was 38.5 to 1. The theoretical molecular weight was 2544. Therewas no added solvent. Similarly, there was no added catalyst. The timeperiod was slightly more than one hour, to wit, 1 /2 hours.

In all succeeding examples the temperature and pressure were the same aspreviously, to wit, 125 C. to 130 C., and not over pounds per squareinch. The time element varied somewhat as noted in succeeding examples.

Example J3 The oxyethylation proceeded in the same manner as describedin Example 31 and J2, preceding. There was no added solvent and no addedcatalyst. The oxide added was one-half of the previous amount, to wit,4.25 pounds. The total oxide at the end of the oxyalkylation procedure34 was 21.25 pounds. The znclal ratio of oxide to condensate was 48to 1. The theoretical molecular weight was 2970. As noted previously,the conditions in regard to temperature and pressure were the same as inregard to Examples lb and 2b. The time period was a little shorter thanbefore, to wit, hour.

Example J4 The oxyethylation was continued and the amount of oxide addedwas the same as before, to wit, 4.25 pounds. The amount of oxide addedat the end of the reaction was 25.5 pounds. There was no added solventand no added catalyst. Conditions as far as temperature and pressurewere concerned were the same as in previous examples. The time periodwas one hour. The molal ratio of oxide to oxyalkylation-susceptiblecompound was 57.8 to l The theoretical molecular weight was 3390.

Example J5 The oxyethylation was continued with the addition of another4.25 pounds of oxide. No added solvent was introduced and likewise noadded catalyst was introduced. The theoretical molecular weight at theend of the reaction was 3812 The molal ratio of oxide tooxyalkylationsusceptible compound was 67.5 to 1. The time period was onehour. The total amount of oxide at the end of the period was 29.75.

Example J6 The oxyalkylation was continued with the addition of the sameamount of oxide as before (4.25 pounds). There was no added solvent andno added catalyst. The amount of oxide in at the end of the reactionperiod was 34 pounds. The theoretical molecular Weight was 4230 and theratio of oxide to oxyalkylation susceptible com pound was 77 to 1. Thetime period was a little longer than previously, to wit, 1 /2 hours.

The same procedure as described in the previous ex: amples was employedin connection with a number of the other condensations describedpreviously. All these data have been presented in tabular form in TablesVIII through X.

In substantially every case a 35-gallon autoclave, was employed,although in some instances the initial oxyethylation was started in aIS-g-allon autoclave and then transferred to a 25-gallon autoclave, orat times to the 35- gallon autoclave. This is immaterial but happened tobe a matter of convenience only. The solvent used in all cases wasxylene. The catalyst used was finely powdered caustic soda.

Referring to Tables VIII, IX, and X, it will be noted that compounds 11through I18 were obtained by the use of ethylene oxide, whereas ExamplesJ 19 through J36 were obtained by the use of propylene oxide; andExample 337 through I54 were obtained by the use of butylene oxide. 7

Referring now to Table IX specifically, it will be noted that the seriesof examples beginning with Kl were obtained, in turn, by use of bothethylene and propylene oxides, using ethylene first; in fact, usingExamples J4- as the oxyalliylation-susceptible compound in the first 6examples. This applies to series K1 through K18.

Similarly, series K19 through K34 involve the use of both propyleneoxide and ethylene oxide in which the propylene oxide was used first, towit, K19 was prepared from J24, a compound which was initially derivedby use of propylene oxide.

Similarly, Examples K37 through K54 involve the, use

of ethylene oxide and butylene oxide, the ethylene, oxidev being usedfirst. Also, these two oxides were used in the series K55 through K72,but in this latter instance the butylene oxide was used first and thenthe ethylene oxide.

Series K73 through K90 involve the use of propylene oxide and butyleneoxide, butylene oxide being used first and propylene oxide being usednext.

In series L1 through L18 the three oxides were used. It will be noted inExample L1 the initial compound was K78; Example K78, in turn, wasobtained from a compound in which butylene oxide was used initially andthen propylene oxide. Thus, the oxide added in the series Ll through L6was by use of ethylene oxideas indicated in Table X.

Referring to Table X, in regard to Example L19 it will be noted againthat the three oxides were used and L19 was obtained from K57. ExampleK57, in turn, was obtained by using butylene oxide first and thenethylene oxide. In Example L19 and subsequent examples, such as L20,L21, etc., propylene oxide was added.

Tables XI, XII, XIII give the data in regard to the oxyalkylationprocedure as far as temperature and pressure are concerned and also givesome data as to solubility of the oxyalkylated derivative in water,xylene and kerosene.

Referring to Table VI'H in greater detail, the data are as follows: Thefirst column gives the example numbers, such as J1, J2, J 3, etc., etc.;the second column gives the oxyalkylation-susceptible compound employedwhich, as previously noted in the series J1 through I6, is Example El,although it would be just as proper to say that in the case of J2 theoxyalkylation-susceptible compound was J1, and in the case of J3 theoxyalkylation-susceptible compound was J2. Actually, reference is to theparent derivative for the reason that the figure stands constant andprobably leads to a more convenient presentation. Thus, the third columnindicates the epoxide-derived condensate previously referred to.

The fourth column shows the amount of ethylene oxide in the mixtureprior to the particular oxyethylation step. In the case of Example J 1there is no oxide used but it appears, of course, in J2, J3, and J 4,etc.

The fifth column can be ignored for the reason that it is concerned withpropylene oxide only, and the sixth column can be ignored for the reasonthat it is concerned with butylene oxide only.

The seventh column shows the catalyst which is invariably powderedcaustic soda. The quantity used is shown.

The eighth column shows the amount of solvent which is xylene unlessotherwise stated.

The ninth column shows the oxyalkylation-susceptible compound which inthis series is a polyepoxide-derived nitrogen compound.

The tenth column shows the amount of ethylene oxide in at the end of theparticular step.

Column eleven shows the same data for propylene oxide and column twelveshows data for butylene oxide. For obvious reasons these can be ignoredin the series Jl through J18.

Column thirteen shows the amount of the catalyst at the end of theoxyalkylation step, and column fourteen shows the solvent at the end ofthe oxyalkylation step.

' The fifteenth, sixteenth and seventeenth columns are concerned withmolal ratio of the individual oxide to the oxyalkylation-susceptiblecompound. Data appears only in column fifteen for the reason, previouslynoted, that no butylene or propylene oxide were used in the presentinstance.

The theoretical molecular weight appears at the end of the table whichis on the assumption, as previously noted, as to the probable molecularweight of the initial compound, and on the assumption that all oxideadded during the period combined. This is susceptible to limitationsthat have been pointed out elsewhere, particularly in the patentliterature.

Referring now to the second series of compounds in Table VIII, to wit,Examples J 19 through J36, the situation is the same except that it isobvious that the oxyalkylating agent used was propylene oxide and notethylene oxide. Thus, the fourth column becomes a blank and the tenthcolumn becomes a blank and the fifteenth column becomes a blank, butcolumn five, which previously was a blank in Table VIII, now carriesdata as to the amount of propylene oxide present at the beginning of thereaction. Column eleven carries data as to the amount of propylene oxidepresent at the end of the reaction, and column sixteen carries data asto the ratio of propylene oxide to the oxyalkylation-susceptiblecompound. In all other instances the various headings have the samesignificance as previously.

Similarly, referring to Examples J37 through J54 in Table VIII, columnsfour and five are blanks, columns ten and eleven are blanks, and columnsfifteen and sixteen are blanks, but data appear in column six as tobutylene oxide present before the particular oxyalkylation step. Columntwelve gives the amount of butylene oxide present at the end of thestep, and column seventeen gives the ratio of butylene oxide tooxyalkylation-susceptible compound.

Table IX is in essence the data presented in exactly the same way exceptthe two oxides appear, to wit, ethylene oxide and propylene oxide. Thismeans that there are only three columns in which data does not appear,all three being concerned with the use of butylene oxide. Furthermore,it shows which oxide was used first by the very fact that reference toExample K1, in turn, refers to J4, and also shows that ethylene oxidewas present at the very first stage. Furthermore, for ease of comparisonand also to be consistent, the data under Molal Ratio in regard toethylene oxide and propylene oxide goes back to the originaldiepoxide-derived compound E1. This is obvious, of course, because thefigures 57.8 and 14.6 coincide with the figures for J 4 derived from E1as shown in Table VIII.

In Table IX the same situation is involved except, of course, propyleneoxide is used first and this, again, is perfectly apparent. Threecolumns only are blank, to wit, the three referring to butylene oxide.The same situation applies in examples such as K37 and subsequentexamples where the two oxides used are ethylene oxide and butylene oxideand the table makes it plain that ethylene oxide was used first.Inversely, Example K55 and subsequent examples show the use of the sametwo oxides but butylene oxide being used first as shown on the ta e.

Example K73 and subsequent examples relate to the use of propylene oxideand butylene oxide. Examples beginning with Ll, Table X, show the use ofall three oxides so there are no blanks as in the first step of eachstage where one oxide is missing. It is not believed any furtherexplanation need be otfered in regard to Table X.

As previously pointed out certain initial runs using one oxide only, orin some instances two oxides, had to be duplicated when usedsubsequently for further reaction. It would be confusing to refer to toomuch detail in these various tables for the reason that all the dataappear in considerable detail and is such that all results can bereadily shown.

Reference to solvent and amount of alkali at any point takes intoconsideration the solvent from the previous step and the alkali leftfrom this step. As previously pointed out, Tables XI, XII and XIII giveoperating data in connection with the entire series, comparable to whathas been said in regard to Examples J1 through J6.

The products resulting from these procedures may con tain modestamounts, or have small amounts, of the solvents as indicated by thefigures in the Tables. If desired, the solvent may be removed bydistillation, and particularly vacuum distillation. Such distillationalso may remove traces or small amounts of uncombined oxide, if

present and volatile under the conditions employed.

37 Obviously, in the use of ethylene ox Needless to say, one could startor, inverse then the other, but one can mix obtain what may be termed anin i.e., no

or any other variant.

ene oxide use ethylene oxide, and then go bac or, one could use acombination in w is use bjec- Theo. mol.

da present alkyl.

ept. mpd.

mount of concenic so Molal ratio PrO a a c trio :1

EtO to oxyto oxyto oxyalkyl. alkyl. suscopt. suscept. susc compd. compd.co

iome

d equal to the caust Solvent, lbs.

55555555555555555555555555555555555.0555555555555555.05580momomoaomnmomfiQmnmQQm&&om&&oo&ow&&oanmOw0wOwowOwomRwodomoaodomoom$o899fl999888888ic aci Catalyst,

lbs.

hat more diificult than ordinarily is the case for if one addshydrochloric acid, for example,

the presence of the alkali unless it is 0 Composition at end B110, lbs.

Generally speaking, the amount of alkaline catalyst to ignore ble orelse add a stoich Oxides PrO, lbs.

7541890J8o0760o754 8 12356 12357 12356 TABLE VIII oso, lbs.

'de and 15 Solvent, lbs.

ixture of ethyllene 0x1 Catalyst, lbs.

13110, lbs.

itrogenous product invariably Oxides PrO, lbs.

Composition before EtO, lbs.

080, lbs.

d along with either one of the two ox The same would be true in regardto a m ene oxide and butylene oxide, or buty propylene oxide.

The colors of the products usually vary from a reddish amber tint to adefinitely red, and amber or a straw color,

Ex. No.

tioned, or a combination of both of them.

or even a pale straw color. The reason is primarily that no efiort ismade to obtain colorless resins initially and 20 the resins themselvesmay be yellow, amber, or even dark amber. Condensation of a 11 yields adarker product than the original resin and usually SL Composition beforeComposition at end p Oxides Oxides M01211 ratio Cata- Sol- Oata- Sol-Theo. S0, lyst, vent, 08C, lyst, vent, EtO PrO BuO mol. lbs. EtO, PrO,BuO, lbs. lbs. lbs. EtO, PrO, BuO, lbs. lbs. to oxyto oxyto oxywt.

lbs. lbs. lbs. lbs. lbs. alkyl. alkyl. alkyl.

suscept. suscept. suscept. compd. compd. compd.

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